CN114100569B - Composite material for extracting lithium and preparation method and application thereof - Google Patents

Composite material for extracting lithium and preparation method and application thereof Download PDF

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CN114100569B
CN114100569B CN202111419743.9A CN202111419743A CN114100569B CN 114100569 B CN114100569 B CN 114100569B CN 202111419743 A CN202111419743 A CN 202111419743A CN 114100569 B CN114100569 B CN 114100569B
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lithium
salt
zeolite
composite material
manganese
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CN114100569A (en
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侯鸿杰
王振青
崔孟涛
郅立鹏
刘冰
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Qingdao Naboke Environmental Protection Technology Co ltd
Qingdao Huashijie Environment Protection Technology Co ltd
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Qingdao Naboke Environmental Protection Technology Co ltd
Qingdao Huashijie Environment Protection Technology Co ltd
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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Abstract

The invention relates to the technical field of composite material preparation, in particular to a composite material for extracting lithium, and a preparation method and application thereof. The composite material comprises zeolite and a manganese lithium ion sieve, and the preparation method comprises the step of loading the manganese lithium ion sieve on porous zeolite. The composite material has simple preparation process and easily controlled parameters, is suitable for industrial production, has good adsorptivity and selectivity to lithium in salt lakes, has extremely low self-dissolution loss rate, and can be used as a means for industrially extracting lithium in salt lakes.

Description

Composite material for extracting lithium and preparation method and application thereof
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a composite material for extracting lithium, and a preparation method and application thereof.
Background
Lithium is the lightest metal in nature and is also the alkali metal with the smallest radius, and the compound has a plurality of excellent performances and has wide and important application in different fields. The lithium resources in nature mainly exist in solid resources such as lithium ores and liquid resources such as salt lakes and seawater, wherein the lithium reserve of the liquid resources is 1.5 ten thousand times of that of the solid resources, so that the lithium resources have extremely important strategic significance for the development of lithium in the liquid. At present, an adsorption method, an extraction method, a dialysis method, an evaporative crystallization method and the like are mainly adopted for extracting lithium from liquid resources, wherein the adsorption method is simple in process, good in selectivity and environment-friendly, and is attractive as a means for extracting lithium with great prospect.
The core of the adsorption method is the selection of adsorbents, which are divided into two major categories, namely high molecular resin and inorganic adsorbents at present, wherein the inorganic adsorbents comprise amorphous hydroxides, layered adsorbents, ion sieve type oxides, aluminum salt adsorbents and the like, and the adsorbents of the types are generally in powder form and have the defect of difficult separation from solution in the process of extracting lithium. Patent CN108212074B discloses a magnetic element doped meta-titanic acid type lithium ion sieve and a preparation method thereof, wherein the method dopes the magnetic element into Li 2 TiO 3 In the crystal lattice of (2), part of titanium is replaced, and lithium is eluted by acid to form the adsorbent prepared by the method, the structure is stable, the separation is easy, but the magnetic material is high in proportion, the adsorption quantity of unit mass is not high, and the parameter control in the preparation process is strict, so that the subsequent industrial production is not facilitated. Patent CN108636344a proposes a preparation method of antimonate adsorbent for salt lake lithium extraction material, dissolving antimonous oxide in strong acid solution, adding silicon oxide to cover hydrogen peroxide aqueous solution, then dripping lithium hydroxide, evaporating and crystallizing, and drying to obtain composite adsorbent.
Disclosure of Invention
The invention aims to provide a composite material for extracting lithium and a preparation method thereof, wherein the preparation method has the advantages of simple process, easily controlled parameters, suitability for industrial production, stable structure of the prepared composite material and easiness in separation from adsorption liquid.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a composite material for extracting lithium comprising zeolite and a manganese-based lithium ion sieve.
The mass ratio of the zeolite is 90-98%, and the mass ratio of the manganese-based lithium ion sieve is 2-10%;
preferably, the mass ratio of the zeolite is 93-96%, and the mass ratio of the manganese-based lithium ion sieve is 4-7%;
more preferably, the mass ratio of the zeolite is 95%, and the mass ratio of the manganese-based lithium ion sieve is 5%.
The specific surface area of the material is 48-55m 2 And/g, the pore diameter is 10-50nm.
The composite material is mainly adsorbed by ion holes generated after lithium is removed from a manganese-based lithium ion sieve, the smaller the aperture is, the larger the specific surface is, the larger the contact surface of the composite material and a solution is, the more favorable for adsorption, but the more difficult the desorption is, so that the aperture and the specific surface are in the range, and the adsorption-desorption balance can be achieved.
The invention also provides a preparation method of the composite material for extracting lithium, which comprises the following steps:
s1: putting zeolite with the grain diameter of 0.15-0.2mm into a chloride salt solution with the mass fraction of 15-25%, boiling for 1-3h, thoroughly washing, and drying at 70-90 ℃ to obtain a zeolite substrate;
preferably, the zeolite is clinoptilolite;
the chloride salt comprises NaCl or KCl;
preferably, the mass fraction of the chloride in the chloride concentrate is 20%;
the mass ratio of the zeolite to the chloride salt is 1:1-5;
preferably, the mass ratio of the zeolite to the chloride salt is 1:3;
preferably, the drying temperature is 80 ℃;
preferably, the boiling time is 2 hours.
The step of boiling can remove impurities in zeolite, and the chloride salt can keep the complete rule of zeolite pore channels, thereby being beneficial to the subsequent loading of the manganese-series lithium ion sieve and the adsorption of lithium in the application process.
S2: preparing lithium salt solution with the concentration of 1-3g/L, adjusting the PH to be acidic, adding manganese salt, adjusting the PH of the mixed solution to be alkaline, and fully stirring at 20-30 ℃ to obtain precursor solution;
the lithium salt comprises one or more of lithium chloride, lithium sulfate and lithium nitrate;
the manganese salt comprises one or more of manganese chloride, manganese sulfate and manganese nitrate;
the lithium salt and the manganese salt are the same anion salt;
the mass ratio of the lithium salt to the manganese salt is 1:18-23;
preferably, the mass ratio of the lithium salt to the manganese salt is 1:20.
Adjusting the pH to be acidic, wherein the pH is adjusted to be 5-5.5 by using an acid corresponding to lithium salt;
adjusting pH to alkaline to 8-8.5 with ammonia water;
preferably, the stirring temperature is 25 ℃;
the solution is neutral or weak alkaline after the lithium salt is dissolved, the lithium salt is in a stable state under the condition, and the reaction activity of the solution can be improved after the pH value is regulated to be acidic; the PH value of the mixed solution after the addition of the manganese salt has a great relationship with the uniformity of the particle size of the manganese lithium ion sieve, and the higher the PH value is, the more favorable the grain growth is, but the uniformity of the grain is reduced at the same time, so that the PH value of the mixed solution is adjusted to 8-8.5. Stirring is required to be fully carried out, and the uniform mixing of the reaction substrates is ensured, so that the grains are as regular as possible.
S3: mixing the zeolite base material with the precursor liquid, reacting for 20-30 hours at 100-130 ℃, filtering, washing and drying to obtain a precursor material;
the mass ratio of the total mass of lithium salt and manganese salt in the precursor solution to the zeolite is 1:20-25;
preferably, the mass ratio of the total mass of lithium salt and manganese salt in the precursor solution to the zeolite is 1:22;
preferably, the reaction temperature is 120 ℃;
preferably, the reaction time is 22h.
S4: and roasting the precursor material at 350-400 ℃ for 20-25h to obtain the composite material for extracting lithium.
Preferably, the firing temperature is 380 ℃.
After the precursor material is roasted, lithium ions in the manganese-series lithium ion sieve generated by bonding lithium ions and manganese ions can be removed, ion holes are formed at the positions, and when the composite material contacts a lithium solution to be extracted, the lithium ions in the solution tend to fill the ion holes on the composite material, so that lithium in the solution is absorbed and extracted by the composite material. After the composite material is adsorbed, desorption is needed to collect lithium, the conventional powder adsorbent is small in particle size, repeated filtration and acid washing are needed, rapid collection is difficult, and the ion sieve provided by the invention is loaded on zeolite with large particle size, so that rapid collection can be performed.
The invention also provides application of the composite material in extracting lithium from salt lakes.
Compared with the prior art, the invention has the following advantages:
(1) The composite material provided by the invention has the advantages that the lithium ion sieve adsorbent is loaded on the porous structure zeolite, the composite material has good selective adsorptivity to lithium ions, and the separation method between the adsorbed lithium ion sieve adsorbent and adsorption liquid is simple, and the desorption rate is high;
(2) The zeolite is a porous material, so that the specific surface of the composite material is further improved, the adsorption capacity is improved, and the method is suitable for industrial lithium extraction;
(3) The composite material has stable structure, cheap raw materials, simple process, easy control of parameters and easy industrialized production.
Drawings
Figure 1 is an XRD spectrum of zeolite in the composite.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The technical solution of the present invention will be described in detail with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
A method for preparing a composite material for extracting lithium, comprising the steps of:
s1: 760g of clinoptilolite with the grain diameter of 0.2mm is put into NaCl solution with the mass fraction of 15 percent to be boiled for 1h, fully washed and dried at the temperature of 70 ℃ to obtain zeolite base material;
the mass ratio of the zeolite to the NaCl is 1:1;
s2: preparing 2g of lithium chloride into 1g/L lithium salt solution, regulating the pH to 5 by using hydrochloric acid, adding 36g of manganese chloride, regulating the pH of the mixed solution to 8 by using ammonia water, and fully stirring at 20 ℃ to obtain a precursor solution;
s3: 760g of zeolite base material is mixed with the precursor liquid, reacted for 20 hours at 100 ℃, filtered, fully washed and dried to obtain a precursor material;
s4: and roasting the precursor material for 20 hours at 350 ℃ to obtain the composite material for extracting lithium.
The prepared composite material for extracting lithium comprises zeolite and a manganese-based lithium ion sieve.
Wherein the mass ratio of the zeolite is 95.2%, and the mass ratio of the manganese lithium ion sieve is 4.8%;
the specific surface area of the composite material is 49.2m 2 And/g, the pore size is concentrated between 22 and 24nm.
XRD characterization is carried out on the zeolite base material in the composite material, as shown in figure 1, the matrix zeolite structure is still complete after modification and loading, the whole process has no influence on zeolite, and the stability of the composite material is shown.
Example 2
A method for preparing a composite material for extracting lithium, comprising the steps of:
s1: putting 1200g of clinoptilolite with the particle size of 0.15mm into a KCl solution with the mass fraction of 25%, boiling for 3 hours, fully washing, and drying at 90 ℃ to obtain a zeolite substrate;
the mass ratio of zeolite to KCl is 1:5;
s2: preparing 2g of lithium sulfate into 3g/L lithium salt solution, regulating the pH to 5 by using sulfuric acid, adding 46g of manganese sulfate, regulating the pH of the mixed solution to 8 by using ammonia water, and fully stirring at 30 ℃ to obtain a precursor solution;
s3: mixing 1200g of zeolite base material with the precursor solution, reacting for 30 hours at 130 ℃, filtering, fully washing, and drying to obtain a precursor material;
s4: and roasting the precursor material at 400 ℃ for 25 hours to obtain the composite material for extracting lithium.
The prepared composite material for extracting lithium comprises zeolite and a manganese-based lithium ion sieve.
Wherein the mass ratio of the zeolite is 96.1 percent, and the mass ratio of the manganese lithium ion sieve is 3.9 percent;
the specific surface area of the composite material is 51.4m 2 And/g, pore size is concentrated at 18-21nm.
Example 3
A method for preparing a composite material for extracting lithium, comprising the steps of:
s1: 924g of clinoptilolite with the grain diameter of 0.18mm is put into KCl solution with the mass fraction of 20 percent to be boiled for 2 hours, fully washed and dried at the temperature of 80 ℃ to obtain zeolite base material;
the mass ratio of zeolite to KCl is 1:3;
s2: preparing 2g of lithium nitrate into 2g/L lithium salt solution, regulating the pH to 5 by using nitric acid, adding 40g of manganese nitrate, regulating the pH of the mixed solution to 8.5 by using ammonia water, and fully stirring at 25 ℃ to obtain a precursor solution;
s3: 924g of zeolite base material is mixed with the precursor liquid, reacted for 25 hours at 120 ℃, filtered, fully washed and dried to obtain a precursor material;
s4: and roasting the precursor material at 380 ℃ for 22 hours to obtain the composite material for extracting lithium.
The prepared composite material for extracting lithium comprises zeolite and a manganese-based lithium ion sieve.
Wherein the mass ratio of the zeolite is 95.7%, and the mass ratio of the manganese lithium ion sieve is 4.3%;
the specific surface area of the composite material is 50.3m 2 And/g, the pore size is concentrated at 15-20nm.
Test example 1
Preparing brine, wherein the content of ions in the brine is Li + (2.125g/L)，Na + (201.361g/L)，K + (48.687g/L)，Mg 2+ (0.013g/L)。
Placing 1g of each of the composite materials prepared in examples 1-3 into 20mL of brine for testing, adsorbing for 2 hours under stirring, taking out the composite material, drying, weighing, pickling with 20mL of pickling solution, pickling for 2 hours under stirring, and testing Li in the adsorbed brine and pickling solution by using a photometer + Is contained in the composition.
The adsorption and desorption results are shown in Table 1.
TABLE 1 adsorption and desorption results
Sequence number Li + Adsorption rate% Dissolution loss rate% Li + Desorption rate% Mg 2+ Adsorption rate%
Example 1 98.9 ≤2.3 97.7 9.9
Example 2 97.6 ≤1.9 97 10.1
Example 3 96.3 ≤1.8 96.2 9.8
The test example shows that the lithium-extracted composite material prepared by the invention has extremely strong adsorption capacity and selectivity on lithium ions, and has extremely strong desorption capacity after adsorption, and the composite material has extremely low dissolution loss rate, can be repeatedly used and has long service life in the process of extracting lithium, and can be proved to be an excellent adsorbent for extracting lithium in salt lakes through the adsorption and desorption rates of lithium ions.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (16)

1. A composite material for extracting lithium, characterized in that the composite material comprises zeolite and a manganese-based lithium ion sieve;
the preparation method of the lithium-extracted composite material comprises the following steps:
s1: putting zeolite into a chloride salt solution, boiling for t1 time, washing and drying to obtain a zeolite substrate;
s2: preparing lithium salt solution, adjusting pH to be acidic, adding manganese salt, adjusting pH of the mixed solution to be alkaline, and stirring at the temperature of T1 to obtain precursor liquid;
s3: mixing a zeolite substrate with a precursor solution, reacting for T2 time at a temperature of T2, filtering, washing and drying to obtain a precursor material;
s4: roasting the precursor material at a temperature of T3 for T3 time to obtain the composite material for extracting lithium;
the temperature of T3 is 350-400 ℃.
2. The composite material according to claim 1, wherein the mass ratio of the zeolite is 90-98%, and the mass ratio of the manganese-based lithium ion sieve is 2-10%.
3. The composite material according to claim 2, wherein the mass ratio of the zeolite is 93-96%, and the mass ratio of the manganese-based lithium ion sieve is 4-7%.
4. A composite material according to claim 3, wherein the zeolite has a mass ratio of 95% and the manganese-based lithium ion sieve has a mass ratio of 5%.
5. The composite material according to claim 1, wherein the specific surface area of the material is 48-55m 2 And/g, the pore diameter is 10-50nm.
6. A method for producing a composite material for extracting lithium according to any one of claims 1 to 5, comprising the steps of:
s1: putting zeolite into a chloride salt solution, boiling for t1 time, washing and drying to obtain a zeolite substrate;
s2: preparing lithium salt solution, adjusting pH to be acidic, adding manganese salt, adjusting pH of the mixed solution to be alkaline, and stirring at the temperature of T1 to obtain precursor liquid;
s3: mixing a zeolite substrate with a precursor solution, reacting for T2 time at a temperature of T2, filtering, washing and drying to obtain a precursor material;
s4: roasting the precursor material at a temperature of T3 for T3 time to obtain the composite material for extracting lithium;
the temperature of T3 is 350-400 ℃.
7. The method of claim 6, wherein step S1 satisfies one or more of the following conditions:
a. the grain diameter of the zeolite is between 0.15 and 0.2 mm;
b. the chloride salt is NaCl or KCl;
c. the mass fraction of the chloride in the chloride solution is 15-25%;
d. the mass ratio of the zeolite to the chloride salt is 1:1-5;
e. the drying temperature is 70-90 ℃;
f. the t1 time is 1-3h.
8. The preparation method according to claim 7, wherein in the step S1, the mass fraction of the chloride in the chloride solution is 20%; the mass ratio of the zeolite to the chloride salt is 1:3; the drying temperature is 80 ℃; the t1 time is 2h.
9. The method of claim 6, wherein step S2 satisfies one or more of the following conditions:
g. the concentration of the lithium salt solution is 1-3g/L;
h. the lithium salt comprises one or more of lithium chloride, lithium sulfate and lithium nitrate;
i. the manganese salt comprises one or more of manganese chloride, manganese sulfate and manganese nitrate;
j. the lithium salt and the manganese salt are the same anion salt;
k. the mass ratio of the lithium salt to the manganese salt is 1:18-23.
10. The method according to claim 9, wherein in step S2, the mass ratio of the lithium salt to the manganese salt is 1:20.
11. The method of claim 6, wherein step S2 further satisfies one or more of the following conditions:
adjusting the pH to be acidic, namely adjusting the pH to be 5-5.5 by using anionic acid corresponding to lithium salt;
adjusting pH to alkaline to 8-8.5 with ammonia water;
and n, the temperature of the T1 is 20-30 ℃.
12. The method according to claim 11, wherein in step S2, the T1 temperature is 25 ℃.
13. The method of claim 6, wherein step S3 satisfies one or more of the following conditions:
the mass ratio of the total mass of lithium salt and manganese salt in the precursor solution to the zeolite is 1:20-25;
p. the temperature of T2 is 100-130 ℃;
and q, wherein the time t2 is 20-30h.
14. The method according to claim 13, wherein in step S3, the mass ratio of the total mass of lithium salt and manganese salt in the precursor solution to the zeolite is 1:22; the temperature of T2 is 120 ℃; the t2 time is 22h.
15. The method of claim 6, wherein step S4 satisfies one or more of the following conditions:
r. the T3 temperature is 380 ℃;
and s, the time t3 is 20-25h.
16. Use of the composite material according to any one of claims 1-5 for extracting lithium from salt lakes.
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CN103121724A (en) * 2012-12-24 2013-05-29 华东理工大学 Method for preparing lithium ion sieve MnO2.0.5H2O and precursor thereof Li1.6Mn1.6O4
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